Bonding and antibonding characters of the first order reduced density matrix. A new look at two charge-shift bonds

Abstract

This article reports a new way of analyzing chemical bonds based on the use of gradient of a first order reduced density matrix (1-RDM) map to partition bonds into atomic core, valence, and dorsal regions that can be further characterized as bonding or antibonding. These classifications are directly related to the familiar language of molecular orbital analysis. Analyses based on these quantities and the critical points of the 1-RDM performed on two charge-shift bonds show that although they share common features, there are fundamental differences in these interactions that are detected neither by density-based analysis nor by valence bond theory. The results suggest the gradient of 1-RDM as a valuable tool in bond analysis.